Reigning champions Real Madrid took advantage of Valencia's defeat to move up to second, a classy Zinedine Zidane volley and two late goals from Raul earning them a 3-1 home win over Racing Santander despite a generally unimpressive performance.
With eight games played, Deportivo lead the standings with 21 points, followed by Real Madrid and Valencia on 19.
While Real produced only flashes of their best form against Racing at a rainswept Bernabeu, Deportivo clinched victory over Valencia with arguably their best performance of the season.
Juan Carlos Valeron hooked in their opener from close range after 14 minutes -- the first goal Valencia had conceded in the league since their opening-day 1-1 draw against Valladolid.
Valencia hit back with a Mista strike after 74 minutes, the former Real Madrid B forward converting a David Albelda cross, but Diego Tristan crashed in a free kick five minutes later to give Deportivo the points.
Real Madrid, missing injured England captain David Beckham, were second best to Racing for all but the final quarter-hour, when the visitors ran out of steam.
"You have to know how to suffer in order to win," said relieved Real coach Carlos Queiroz.
"We played with intelligence, patience and a lot of sacrifice."
DARING RACING
Most teams this season have come to the Bernabeu with a damage limitation exercise in mind but Racing took the game to Real from the start.
With Fernando Moran, Rodolfo Bodipo and Yossi Benayoun in eye-catching form, Racing carved the Real defence apart repeatedly, only for poor finishing to let them down.
Their goal came just past the quarter-hour when Moran ran with the ball across the front of the Real area and picked out Benayoun in the centre who turned and fired past Iker Casillas.
A Casillas flap from a corner almost led to a second Racing goal but the Real defence scrambled the ball clear.
Racing passed the ball better than their illustrious opponents and created a string of chances but they failed to extend their lead and paid the price in the 27th when Zidane produced a precise volley from Ronaldo's cross.
Real only threatened to take the lead with a couple of free kicks before Raul's tap-in in the 78th minute made it 2-1.
Racing pressed forward for an equaliser only to be hit again late on, with Raul turning in after Santiago Solari's shot had been deflected.